EP2456792B1 - Process for the production of condensation polymers via in-reactor chain extension and products thereof - Google Patents

Process for the production of condensation polymers via in-reactor chain extension and products thereof Download PDF

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EP2456792B1
EP2456792B1 EP10802839.0A EP10802839A EP2456792B1 EP 2456792 B1 EP2456792 B1 EP 2456792B1 EP 10802839 A EP10802839 A EP 10802839A EP 2456792 B1 EP2456792 B1 EP 2456792B1
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acrylate
methacrylate
chain
meth
condensation polymer
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EP2456792A4 (en
EP2456792A2 (en
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Gary A. Deeter
Marco A. Villalobos
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BASF Corp
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BASF Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C08F212/10—Styrene with nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate

Definitions

  • condensation or step-growth polymers including polyesters, polyamides, and polycarbonates
  • plastic products such as films, bottles, and other molded products.
  • the mechanical and physical properties of these polymers are highly dependent on their molecular weights.
  • Much effort has been placed on developing the next generation polycondensates by increasing molecular weight and introducing branching.
  • increasing molecular weight during the initial polymerization process generally requires long reaction times and high temperatures, resulting in polymer degradation, poor application performance, and poor finished part appearance.
  • reactor limitations restrict the maximum molecular weights that can be achieved during the initial polymerization process thereby limiting the range of applications of such polymers.
  • Solid state polymerization may be used to further process the synthesized polymer and increase molecular weight.
  • SSP is time consuming and expensive.
  • polycondensation reactions are reversible and subject to dynamic equilibrium at higher reactive group conversion and polycondensate molecular weight. Constant removal of condensation product(s) becomes necessary in order to displace equilibrium towards products thus enhancing forward reaction rates, increasing product molecular weight and reactor productivity. Operation at high temperatures and extreme vacuum conditions are necessary to eliminate condensation products from the reaction mix, to achieve higher molecular weights (or intrinsic viscosity, I.V.) in a suitable time. Given the asymptotic nature of the polycondensate molecular weight increase with reaction time, attempts to produce higher molecular weight products result in longer reaction times, decreases in reactor productivity, and added energy and labor costs. Higher molecular weights are desirable for higher product performance, yet unattainable economically with the current art. Moreover, it is known in the art that extended polymerization times lead to a variety of degradation by-products that affect the performance and appearance of these products.
  • Document WO 03/066704 discloses chain extenders which are identical to the present compounds and which are used to extend the chains of polymers such as polyesters, polyamides or polycarbonates.
  • Document US2004147678 has an equivalent disclosure.
  • the present method differs from the method of WO 03/066704 in that the chain extender is added to the polymerization mixture during polymerization of the condensation polymer.
  • the finished condensation polymer and the chain extender are mixed and treated in an extruder where depolymerisation and chain extension simultaneously take place.
  • methods for making condensation polymers involve adding certain polymeric chain extenders during the polymerization process of the condensation polymer to provide a chain-extended condensation polymer.
  • the methods are capable of reducing the polymerization times and/or increasing the molecular weight for the chain-extended condensation polymer as compared to the polymerization times for the condensation polymer formed in the absence of the chain extenders.
  • the methods provide chain-extended condensation polymers having high molecular weights using shorter polymerization times than previously possible. Consequently, such methods increase the efficiency and capacity of polymerization plants employing the methods, resulting in significant cost savings.
  • polymerization times are reduced, it is possible to avoid one or more of the polymer degradation, poor application performance, and poor finished part appearance associated with polymers formed using conventional methods having long reaction times and high temperatures.
  • the disclosed methods provide chain-extended condensation polymers having high molecular weights, the methods are capable of reducing the SSP polymerization times for the processed, chain-extended condensation polymers as compared to the SSP polymerization times for the processed, condensation polymer formed in the absence of the chain extenders.
  • the methods involve adding a chain extender during the polymerization process of a condensation polymer to provide a chain-extended condensation polymer.
  • the chain extender includes a polymerization product of at least one functional (meth)acrylic monomer being epoxy-, anhydride-, carboxylic-, an hydroxy-functional and at least one styrenic and/or (meth)acrylic monomer.
  • a method including adding a chain extender during the polymerization process of a condensation polymer to provide a chain-extended condensation polymer, wherein the chain extender includes a polymerization product of at least one functional (meth)acrylic monomer according to claim 1, and at least one styrenic and/or (meth)acrylic monomer.
  • the at least one functional (meth)acrylic monomer includes at least one functional group selected from an epoxy group, an anhydride group, a carboxylic acid group, and a hydroxyl group.
  • the chain extender has a functionality of 2 or more. In some embodiments, the chain extender has a functionality of from 2 to 30.
  • the chain extender has a functionality of greater than 2. In some embodiments, the chain extender has a functionality of greater than 2, but less than or equal to 30.
  • the functional (meth)acrylic monomer is an epoxy-functional (meth)acrylic monomer. In some embodiments, the epoxy-functional (meth)acrylic monomer is glycidyl methacrylate.
  • the styrenic monomer is styrene and the (meth)acrylic monomer is selected from butyl acrylate, 2-ethylhexyl acrylate, or methyl (meth)acrylate.
  • the at least one functional (meth)acrylic monomer is present in an amount of 0.5% to 75% by weight of the total weight of the monomers in the chain extender.
  • the at least one styrenic and/or (meth)acrylic monomer is present in an amount of 95.5% to 25% by weight of the total weight of the monomers in the chain extender.
  • the chain extender is added to the condensation polymer in an amount of 0.03% to 10% by weight of the total weight of the chain extender and the components of the condensation polymer.
  • the condensation polymer is selected from polyesters, polyamides, or polycarbonates. In some embodiments, the condensation polymer is a polyester. In some embodiments, the condensation polymer is a bio-polyester. In some embodiments, the bio-polyester is selected from poly(lactic acid), poly(2-hydroxybutyric acid), or other biopolyesters including the polymerization products of monomers with the general formula CH 3 -CH(OH)-(CH 2 ) n -COOH or CH 2 (OH)-(CH 2 ) n -COOH, where n is greater than, or equal to, one. For example, in some embodiments, n is from one to about 20. In other embodiments, n is from one to about 10.
  • the polyester is selected from poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene naphthalate), or poly(butylene naphthalate), poly(lactic acid), poly(2-hydroxybutyric acid), or other poly(hydroxyalkyl acid) per the general formula of CH 3 -CH(OH)-(CH 2 ) n -COOH or CH 2 (OH)-(CH 2 ) n -COOH.
  • a method including, adding a chain extender during the polymerization process of a polyester to provide a chain-extended polyester, wherein the chain extender includes a polymerization product of at least one epoxy-functional (meth)acrylic monomer, and at least one styrenic and/or (meth)acrylic monomer.
  • the chain extender is added when the solution intrinsic viscosity of the condensation polymer is no more than 0.6 dL/g.
  • a molecular weight of the chain-extended condensation polymer is achieved in a time that is less than the time to achieve the molecular weight in the absence of the chain extender.
  • the time is at least 10% less.
  • a solution intrinsic viscosity of at least 0.6 dl/g of the chain-extended condensation polymer is achieved in a time of 90 minutes or less.
  • the method further includes processing the chain-extended condensation polymer via solid state polymerization.
  • a molecular weight of the processed, chain-extended condensation polymer is achieved in a time that is less than the time to achieve the molecular weight in the absence of the chain extender. In some embodiments, the time is at least 5% less than the time to achieve the molecular weight in the absence of the chain extender.
  • a solution intrinsic viscosity of at least 0.8 dl/g of the processed, chain-extended condensation polymer is achieved in a time of 15 hours or less. In some embodiments, the chain-extended condensation polymer exhibits a greater melt viscosity than a condensation polymer formed in the absence of the chain extender.
  • the chain-extended condensation polymer exhibits a higher viscosity at low shear rates and a lower viscosity at high shear rates than a condensation polymer formed in the absence of the chain extender. In some embodiments, the chain-extended condensation polymer exhibits a higher viscosity at shear rates below 200 s -1 and a lower viscosity at shear rates above 500 s -1 as compared with a condensation polymer formed in the absence of the chain extender.
  • a method including adding a chain extender during the polymerization process of a polyester to provide a chain-extended polyester, wherein the chain extender comprises a polymerization product of at least one epoxy-functional (meth)acrylic monomer, and at least one styrenic, a (meth)acrylic monomer, or a mixture thereof; where the polymerization process is a batch polymerization process or a continuous polymerization process; the chain extender is added when the solution intrinsic viscosity of the condensation polymer is no more than 0.6 dL/g; and a molecular weight of the chain-extended condensation polymer is achieved in a time that is less than the time to achieve the molecular weight in the absence of the chain extender.
  • the time is at least 10% less.
  • a solution intrinsic viscosity of at least 0.6 dl/g of the chain-extended condensation polymer is achieved in a time of 90 minutes or less.
  • a solution intrinsic viscosity of at least 0.8 dl/g of the processed, chain-extended condensation polymer is achieved in a time of 15 hours or less.
  • the chain-extended condensation polymer exhibits a greater melt viscosity than a condensation polymer formed in the absence of the chain extender.
  • the chain-extended condensation polymer exhibits a higher viscosity at low shear rates and a lower viscosity at high shear rates than a condensation polymer formed in the absence of the chain extender.
  • the chain extender has a functionality of 2 or more.
  • the epoxy-functional (meth)acrylic monomer is glycidyl methacrylate.
  • the styrenic monomer is styrene, and the (meth)acrylic monomer is butyl acrylate, 2-ethylhexyl acrylate, or methyl (meth)acrylate.
  • At least one functional (meth)acrylic monomer is present in an amount of 0.5% to 75% by weight of the total weight of the monomers in the chain extender. In some embodiments, the at least one styrenic and/or (meth)acrylic monomer is present in an amount of 95.5% to 25% by weight of the total weight of the monomers in the chain extender. In some embodiments, the chain extender is added to the condensation polymer in an amount of 0.03% to 10% by weight of the total weight of the chain extender and the components of the condensation polymer. In some embodiments, the condensation polymer is selected from polyesters, polyamides, polycarbonates, or a bio-polyester.
  • chain-extended condensation polymers made by any of the disclosed methods are also provided. Due to the reduction in polymerization times (including SSP polymerization times), the chain-extended condensation polymers (including SSP processed, chain-extended condensation polymers) have minimal amounts of by-products normally associated with conventional of high molecular weight condensation polymers. Despite the increased branching associated with certain of the chain-extended condensation polymers, the mechanical and thermal properties of these polymers are surprisingly similar to those of condensation polymers formed in the absence of the chain extenders when at the same target molecular weight (or I.V.). However, the chain-extended condensation polymers exhibit unique rheological properties as compared to condensation polymers formed in the absence of the chain extender. These properties are further described below.
  • the methods include adding a chain extender during the polymerization process of a condensation polymer to provide a chain-extended condensation polymer.
  • the chain extender includes a polymerization product of at least one functional (meth)acrylic monomer according to claim 1 and at least one styrenic and/or (meth)acrylic monomer.
  • the phrase "in-reactor chain extension” is also used herein to refer to the method of adding any of the disclosed chain extenders during the polymerization process of a condensation polymer to provide a chain-extended condensation polymer.
  • the disclosed chain extenders include a polymerization product of at least one functional (meth)acrylic monomer and at least one styrenic and/or (meth)acrylic monomer.
  • the functional (meth)acrylic monomer the functional group is selected from an epoxy group, an anhydride group, a carboxylic acid group, and a hydroxyl group.
  • the use of a particular functional group can depend upon the identity of the condensation polymer.
  • certain polyesters include aliphatic hydroxyl and/or aromatic or aliphatic carboxylic acid chain ends.
  • Functional (meth)acrylic monomers having epoxy groups, anhydride groups, or carboxylic acid groups are capable of reacting with such polyesters.
  • Polycarbonates include phenolic chain ends.
  • Functional (meth)acrylic monomers having epoxy groups, anhydride groups, or carboxylic acid groups are capable of reacting with such polycarbonates.
  • Polyamides include amine and carboxylic acid chain ends.
  • Functional (meth)acrylic monomers having epoxy groups, anhydride groups, or carboxylic acid groups are capable of preferentially reacting with amine chain ends;
  • functional (meth)acrylic monomers having hydroxyl groups are capable of reacting with the carboxylic acid chain ends;
  • functional (meth)acrylic monomers having epoxy groups are capable of reacting with both types of chain ends.
  • carboxyl-containing radically-polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, and maleic acid.
  • anhydride-containing radically-polymerizable monomers include maleic anhydride, itaconic anhydride and citraconic anhydride.
  • Hydroxy-containing radically-polymerizable monomers that can be used in the process include hydroxy acrylates and methacrylates such as 2-hydroxy ethyl methacrylate, 2-hydroxy ethyl acrylate, hydroxy propyl acrylate, 3-chloro-2-hydroxy-propyl acrylate, 2-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, 2-hydroxymethyl methacrylate, 2-hydroxypropyl methacrylate, 6-hydroxyhexyl methacrylate, and 5,6-dihydroxyhexyl methacrylate.
  • hydroxy acrylates and methacrylates such as 2-hydroxy ethyl methacrylate, 2-hydroxy ethyl acrylate, hydroxy propyl acrylate, 3-chloro-2-hydroxy-propyl acrylate, 2-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, 2-hydroxymethyl methacrylate, 2-hydroxypropyl methacrylate, 6-hydroxyhexyl methacrylate,
  • Examples of amine-containing radically-polymerizable monomers include 2-(diethylamino)ethyl acrylate, 2-(dimethylamino) ethyl acrylate, 2-(dimethylamino)propyl acrylate, 2-(diethylamino)ethyl methacrylate, 2-(dimethylamino)ethylmethacrylate, 2-dimethylamino)propyl acrylate.
  • Still other radically-polymerizable monomers containing condensation reactive functionalities include amides such as acrylamide, N-ethyl acrylamide, N,N-diethyl acrylamide methacrylonitrile, methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N,N-diethyl methacrylamide, N,N-dimethyl methacrylamide, and N-phenyl methacrylamide.
  • the functional group is an epoxy group and the functional (meth)acrylic monomer is an epoxy-functional (meth)acrylic monomer.
  • epoxy-functional includes both epoxides and functional equivalents of such materials, such as oxazolines.
  • examples of epoxy-functional (meth)acrylic monomers include those containing 1,2-epoxy groups such as glycidyl acrylate and glycidyl methacrylate.
  • Other suitable epoxy-functional monomers include allyl glycidyl ether, glycidyl ethacrylate, glycidyl itoconate, and other glycidyl (meth)acrylates
  • the functionality of the disclosed chain extenders may vary.
  • the chain extenders are characterized by having a broad range of epoxy equivalent weight (EEW) values from moderately low to very high.
  • the functionality of the chain extenders is 2 or greater.
  • the functionality of the chain extenders is greater than 2.
  • Such multifunctional chain extenders are capable of reacting with certain groups on the disclosed condensation polymers, leading to an increased rate of linear chain growth if the functionality equals 2, or branching if the functionality is greater than 2.
  • epoxy-functional (meth)acrylic monomers are capable of reacting with the hydroxyl (OH) and/or carboxylic acid (COOH) ends of a polyester.
  • FIG. 1 illustrates an exemplary reaction between poly(ethylene terephthalate) (D) and an exemplary epoxy-functional chain extender (E) to form a chain-extended polyester (F).
  • the epoxy-functional (meth)acrylic monomers react preferentially with carboxylic acid groups and have a functionality greater than 2, predominantly leading to chain branching as shown in FIG. 1 .
  • the term (meth)acrylic includes both acrylic and methacrylic monomers.
  • Examples of (meth)acrylic monomers include both acrylates and methacrylates.
  • Suitable acrylate and methacrylate monomers for use in the chain extenders include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, methylcyclohexyl acrylate, cyclopentyl acrylate, methylcyclohe
  • suitable monomers include styrene, ⁇ -methyl styrene, vinyl toluene, p-methyl styrene, t-butyl styrene, o-chlorostyrene, vinyl pyridine, and mixtures of these species.
  • the styrenic monomer is styrene.
  • the disclosed chain extenders may include various amounts of the functional (meth)acrylic monomer and the styrenic and/or (meth)acrylic monomers.
  • the at least one functional (meth)acrylic monomer is present in an amount of 0.5% to 75% by weight of the total weight of the monomers in the chain extender. This includes embodiments in which the at least one functional (meth)acrylic monomer is present in an amount of 10% to 70%, 15% to 60%, or 20% to 50%. However, other amounts are possible.
  • the at least one styrenic and/or (meth)acrylic monomer is present in an amount of 95.5% to 25% by weight of the total weight of the monomers in the chain extender. This includes embodiments in which the at least one styrenic and/or (meth)acrylic monomer is present in an amount of 90% to 30%, 80% to 40%, or 70% to 50%. However, other amounts are possible.
  • the molecular weight of the chain extenders may vary.
  • the number average molecular weight of the chain extenders may range from 1,000 to 10,000. This includes embodiments in which the molecular weight ranges from 1,500 to 5,000, from 2,000 to 7,000, or from 3,000 to 9,000. However, other molecular weights are possible.
  • the weight average molecular weight of the chain extenders may range from 1,500 to 35,000. This includes embodiments in which the molecular weight ranges from 2,500 to 15,000, from 5,000 to 20,000, or from 10,000 to 30,000. However, other molecular weights are possible.
  • the desired epoxy equivalent weight (EEW) is fixed by the desired content of the epoxy-functional (meth)acrylic monomer employed.
  • the number average epoxy functionality per chain (Efn) can be tailored from very low ( e.g., ⁇ 1) to very high ( e.g., >30) by controlling the number average molecular weight (M n ) of the chain extender.
  • PDI can be tailored from very low ( e.g., 1.5) to very high ( e.g ., 5).
  • chain extenders may be used, including those described in U.S. Pat. Nos. 6,552,144 , 6,605,681 and 6,984,694 .
  • the disclosed chain extenders may be produced according to standard techniques known in the art. Such techniques include known high temperature, free radical continuous polymerization processes. Briefly, these processes involve continuously charging into a reactor at least one functional (meth)acrylic monomer, at least one styrenic and/or (meth)acrylic monomer, and optionally at least one free radical polymerization initiator. The proportion of monomers charged into the reactor may be the same as those proportions that go into the chain extenders discussed above.
  • the reactor may also optionally be charged with at least one free radical polymerization initiator.
  • the initiators suitable for carrying out the process are compounds which decompose thermally into radicals in a first order reaction, although this is not a critical factor. Suitable initiators include those with half-life periods in the radical decomposition process of 1 hour at temperatures greater or equal to 90 °C and further include those with half-life periods in the radical decomposition process of 10 hours at temperatures greater than, or equal to, 100 °C. Others with about 10 hour half-lives at temperatures significantly lower than 100° C may also be used.
  • Suitable initiators include aliphatic azo compounds such as 1-t-amylazo-1-cyanocyclohexane, azo-bis-isobutyronitrile and 1-t-butylazo-cyanocyclohexane, 2,2'-azo-bis-(2-methyl)butyronitrile and peroxides and hydroperoxides, such as t-butylperoctoate, t-butyl perbenzoate, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, and di-t-amyl peroxide. Additionally, di-peroxide initiators may be used alone or in combination with other initiators.
  • Such di-peroxide initiators include 1,4-bis-(t-butyl peroxycarbo)cyclohexane, 1,2-di(t-butyl peroxy)cyclohexane, and 2,5-di(t-butyl peroxy)-3-hexyne, and other similar initiators.
  • the initiator may be added with the monomers and may be added in any appropriate amount.
  • the total initiators are added in an amount of 0.0005 to 0.06 moles initiator(s) per mole of monomers in the feed.
  • the initiator may be admixed with the monomer feed or added to the process as a separate feed.
  • the reactor may also optionally be charged with one or more solvents fed into the reactor together with the monomers, or in a separate feed.
  • the solvent may be any solvent known in the art, including those that do not react with the functional group on the functional (meth)acrylic monomer at the high temperatures of the continuous process described herein. The proper selection of solvent may help decrease or eliminate the gel particle formation during the continuous, high temperature reaction.
  • Such solvents include xylene; toluene; ethyl-benzene; Aromatic-100 ® , Aromatic 150 ® , Aromatic 200 ® , all of which are available from Exxon; acetone; methylethyl ketone; methyl amyl ketone; methyl-isobutyl ketone; n-methyl pyrrolidinone; and combinations of any two or more such solvents.
  • the solvents are present in any amount desired, taking into account reactor conditions and monomer feed. In one embodiment, one or more solvents are present in an amount of up to 40% by weight, or up to 15% by weight, in other embodiments, based on the total weight of the monomers.
  • the reactor is maintained at an effective temperature for an effective period of time to cause polymerization of the monomers to produce the polymerized chain extender.
  • the continuous polymerization is carried out at high temperatures.
  • the polymerization temperatures range from 160 °C to 270 °C. This includes embodiments where the temperatures range from 170 °C to 250 °C or from 170 °C to 232 °C. This also includes embodiments where the temperatures range from 175 °C to 250 °C or from 180 °C to 232 °C.
  • a continuous polymerization process allows for a short residence time within the reactor.
  • the residence time is generally less than about one hour, and may be less than 15 minutes. In some embodiments, the residence time is generally less than 30 minutes, and may be less than 20 minutes.
  • the process for producing the chain extenders may be conducted using any type of reactor known in the art, and may be set up in a continuous configuration.
  • reactors include, but are not limited to, continuous stirred tank reactors ("CSTRs"), tube reactors, loop reactors, extruder reactors, or any reactor suitable for continuous operation.
  • CSTRs continuous stirred tank reactors
  • tube reactors tube reactors
  • loop reactors loop reactors
  • extruder reactors any reactor suitable for continuous operation.
  • a form of CSTR which has been found suitable for producing the chain extenders is a tank reactor provided with cooling coils and/or cooling jackets sufficient to remove any heat of polymerization not taken up by raising the temperature of the continuously charged monomer composition so as to maintain a preselected temperature for polymerization therein.
  • Such a CSTR may be provided with at least one, and usually more, agitators to provide a well-mixed reaction zone.
  • Such a CSTR may be operated at varying filling levels from 10 to 100% full (liquid full reactor LFR). In one embodiment, the reactor is 100% liquid full.
  • condensation polymers are polyesters (PEs), polyamides (PAs), and polycarbonates (PCs).
  • Polyesters include homo- or copolyesters that are derived from aliphatic, cycloaliphatic or aromatic dicarboxylic acids and diols or hydroxycarboxylic acids.
  • Non-limiting, exemplary polyesters include poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), poly(ethylene naphthalate) (PEN), and poly(butylene naphthalate).
  • PET poly(ethylene terephthalate)
  • PBT poly(butylene terephthalate)
  • PEN poly(ethylene naphthalate)
  • the application of these and other polyesters is broad and includes textile fibers, food packaging, beverage containers, electrical connectors and housings, or tire cord.
  • Polyamides include polyamides produced by polycondensing a dicarboxylic acid with a diamine, polyamides produced by polymerizing a cyclic lactam, and polyamides produced by co-polymerizing a cyclic lactam with a dicarboxylic acid/diamine salt.
  • the polyamides include polyamide elastomer resins. Suitable polyamide elastomer resins include nylon 6, nylon 6-6, nylon 6-10, nylon 11, nylon 12, and co-polymers and blends of any two or more such polyamides.
  • Polycarbonates include aromatic polycarbonates produced by reactions of bisphenols with carbonic acid derivatives such as those made from bis-phenol A (2,2-bis(4-hydroxyphenyl)propane) and phosgene or diphenyl carbonate.
  • carbonic acid derivatives such as those made from bis-phenol A (2,2-bis(4-hydroxyphenyl)propane) and phosgene or diphenyl carbonate.
  • Polyestercarbonates made from one or more aromatic dicarboxylic acids or hydroxycarboxylic acids, bisphenols and carbonic acid derivatives are also included.
  • Polycarbonate resins may also be prepared from bis-phenol A and carbonic acid derivatives.
  • the condensation polymer is a polyester. In some such embodiments, the condensation polymer is selected from poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene naphthalate), or poly(butylene naphthalate). In some embodiments, the condensation polymer is poly(ethylene terephthalate) (PET).
  • PET poly(ethylene terephthalate)
  • the raw materials used in the polymerization of PET are a mixture of aromatic diacids (A) [terephthalic acid (PTA; 1, 4-substitution) and isophthalic acid (IPA; 1, 3-substitution)] and ethylene glycol (B).
  • the aromatic diacid (A) mol ratio is manipulated to control crystallinity.
  • the diacid (A) to glycol (B) mol ratio is adjusted to minimize deleterious side reactions, tailor polymer properties, and maximize production efficiency.
  • the polymerization process consists of two stages. Stage 1 is esterification or pre-polycondensation (Equation 1), which can be separated into pressurized and ambient esterification. Early in stage 1, high pressures are used to prevent glycol loss to maintain stoichiometry.
  • Stage 1 yields PET oligomers consisting of five to twelve repeat units (C).
  • Stage 2 is polycondensation (Equation 2) and uses very high vacuum and temperature and catalysts. Table 1 lists the catalyst and preservative package, the aromatic diacid (A) to glycol (B) mol ratios, and the PTA to IPA mol ratios used in the Examples described below. Tetramethyl ammonium hydroxide (TMAH) was used to prevent polyethylene glycol formation, antimony trioxide (Sb 2 O 3 ) was used as a polymerization catalyst, cobalt [II] acetate tetrahydrate was added to reduce color, and phosphoric acid as an antioxidant to improve color and thermal stability.
  • TMAH Tetramethyl ammonium hydroxide
  • SB 2 O 3 antimony trioxide
  • cobalt [II] acetate tetrahydrate was added to reduce color
  • phosphoric acid as an antioxidant to improve color and thermal stability.
  • PET is prepared to a solution intrinsic viscosity (SIV) of approximately 0.6 dL/g, which is equivalent to a molecular weight between 25,000 and 30,000.
  • SIV solution intrinsic viscosity
  • SSP solid state polymerization
  • the condensation polymer is a polyamide.
  • Polyamides can be produced by batch or continuous polymerization processes.
  • the chain extenders can also be used with polyamides.
  • the condensation polymer is a polycarbonate.
  • Polycarbonates can be produced by batch or continuous polymerization processes.
  • the chain extenders can also be used with polycarbonates.
  • any of the described chain extenders are added to any of the described condensation polymers during the polymerization process of the condensation polymer to provide a chain-extended condensation polymer.
  • the phrase "during the polymerization process” means during the initial synthesis process by which the condensation polymers are formed. This phrase excludes adding the chain extenders before, or during, subsequent processing of the polymerized condensation polymers, such as processing by SSP. Methods in which chain extenders are added before or during a subsequent processing step, such as SSP, are possible, but such methods are described separately below.
  • the polymerization process may be a batch polymerization process or a continuous polymerization process.
  • An exemplary batch polymerization process for PET has been described above and shown in Scheme 1.
  • methods e.g ., reactors and reactor conditions
  • An exemplary polymerization process for PET is further described in the Examples below.
  • the disclosed chain extenders may be added at various times during the polymerization process of the condensation polymers.
  • the chain extenders may be added during the pre-polycondensation stage, the polycondensation stage, or both. In some embodiments, the chain extenders are added during the polycondensation stage.
  • the chain extenders are added at the point during the polymerization process at which the condensation polymers have achieved a particular solution intrinsic viscosity (SIV).
  • SIV solution intrinsic viscosity
  • the chain extender is added when the SIV of the condensation polymer is no more than 0.6 dL/g. In other embodiments, the chain extender is added when the SIV of the condensation polymer is no more than 0.5 dL/g, 0.4 dL/g, or 0.3 dL/g.
  • SIVs solution intrinsic viscosity
  • Adding the chain extenders while the SIV of the condensation polymer is relatively low may be useful because the processing temperatures tend to be lower (decreasing degradation) and it is easier to thoroughly mix the chain extenders (increasing reaction efficiency).
  • the concentrations of the reactive end groups of the condensation polymers are relatively high (increasing reaction efficiency).
  • the chain extenders can also be used in various continuous polymerization processes for making condensation polymers.
  • the chain extenders can be added to the inlet stream of a continuous melt polymerization reactor after the esterification reactor.
  • chain extender can be continuously added into an intermediate reactor location when available in the continuous melt polymerization reactor. This is equivalent to adding it at some intermediate point during the batch melt polymerization time.
  • the chain extender should be added at a suitable time or reactor place when the SIV of the material in the melt polymerization reactor is between 0.20 and 0.55, between 0.25 and 0.50, between 0.30 and 0.45, or between 0.35 and 0.45, according to various embodiments.
  • the chain extenders may be added to the condensation polymers at various amounts.
  • the chain extenders are added in an amount ranging from 0.03% to 10% by weight of the total weight of the chain extender and the components of the condensation polymer.
  • components of the condensation polymer it is meant the components that are added to the feed to produce the condensation polymer. This includes embodiments in which the amount ranges from 0.05% to 5%, from 0.075% to 3%, and from 0.1% to 1%. However, other amounts are possible. The particular amount depends upon the identity of the chain extender, the identity of the condensation polymer, and the desired amount of molecular weight gain and/or branching.
  • the methods further include processing the chain-extended condensation polymer via SSP.
  • Suitable reactors and reactor conditions for SSP are known.
  • additional chain extenders may be added to the chain-extended polymers prior to or during the SSP processing.
  • processed, chain-extended condensation polymer is used to refer to a condensation polymer that has been subjected to both in-reactor chain extension and SSP.
  • the methods may further include a variety of plastic forming operations, including injection-blow molding, extrusion-blow molding, sheet and film extrusion, injection molding, thermoforming, film-blowing, and fiber spinning. Apparatuses and processing conditions for these operations are known. Any of the methods may also be followed by a polymer recovery and a pelletization stage to obtain pellets or granules of the chain-extended or processed, chain-extended condensation polymer.
  • the disclosed methods provide a number of processing advantages compared to conventional methods of forming condensation polymers. As noted above, the disclosed methods are capable of reducing the polymerization times for the chain-extended condensation polymers as compared to the polymerization times for condensation polymers formed in the absence of the chain extenders. However, it is noted that the disclosed chain extenders do not affect polymerization reaction kinetics- i.e., the chain extenders are not catalysts. During melt polymerization, chain extension occurs regardless of the specific catalyst system employed. For example, in the preparation of polyester, metal-based oxides are traditionally employed as catalysts. Metal-based oxides of antimony, titanium, aluminum, zirconium, germanium, and other metals may be used as the catalyst. Because the chain extension described here is not based upon catalytic mechanisms, chain extension occurs independently of the polyester formation. The same is true for the preparation of bio-polyesters, polyamides and polycarbonate reaction systems.
  • the chain extenders dramatically increase the instantaneous molecular weight of the condensation polymers upon addition of the chain extenders.
  • time it is meant the time of residence in the polymerization reactor regardless of the type of operation (batch, semi-continuous, or continuous).
  • the time is at least 10% less.
  • the time is at least 15% less, 20% less, 25% less, 30% less, 35% less, 40% less, 50% less, 60% less, 70% less, 80% less, or 90% less.
  • the time is at least 50% less.
  • the Examples below describe how to measure the reduction in polymerization times and monitor molecular weights by measuring agitator torque and speed versus time during the polymerization process. Molecular weight may also be monitored by measuring solution intrinsic viscosity and melt viscosity according to known methods. In some embodiments, the disclosed methods are capable of providing chain-extended condensation polymers having higher molecular weights than is possible using conventional methods of forming condensation polymers in the absence of the disclosed chain extenders.
  • the methods are capable of achieving certain solution intrinsic viscosities of the chain-extended condensation polymers in reduced times.
  • a solution intrinsic viscosity of at least 0.6 dL/g of the chain-extended condensation polymer is achieved in a time of no more than 90 minutes. This includes embodiments in which the time is no more than 85 minutes, no more than 80 minutes, no more than 75 minutes, or no more than 70 minutes.
  • the reduction in polymerization times has a number of important advantages.
  • the capacity of a typical polymerization plant running under typical conditions may be increased by at least 10%, 20%, 30%, 40%, 50%, or even more, using the disclosed methods.
  • the methods are capable of reducing the SSP polymerization times for the processed, chain-extended condensation polymers as compared to the SSP polymerization times for the processed, condensation polymer formed in the absence of the chain extenders.
  • it is possible to achieve a molecular weight of the processed, chain-extended condensation polymer in a time that is less than the time to achieve the molecular weight in the absence of the chain extender.
  • the time is at least 5% less. In other embodiments, the time is at least 10%, 15%, 20% less, or more.
  • the methods are capable of achieving certain solution intrinsic viscosities of the processed, chain-extended condensation polymers in reduced times.
  • a solution intrinsic viscosity of at least 0.8 dL/g of the processed, chain-extended condensation polymer is achieved in a time of 15 hours or less. This includes embodiments in which the time is 14 hours, 13 hours, 12 hours, or less.
  • chain-extended and processed, chain-extended condensation polymers formed by the disclosed methods exhibit a number of desirable characteristics.
  • changes in the mechanical and thermal properties of such polymers would be expected.
  • the mechanical and thermal properties of such polymers are not negatively affected as compared to condensation polymers formed in the absence of the disclosed chain extenders.
  • the chain-extended condensation polymers have advantageous rheological properties. As further described in the Examples below, in some embodiments, the chain-extended condensation polymers exhibit a greater melt viscosity than a condensation polymer formed in the absence of the chain extenders. In some such embodiments, the melt viscosity is at least 1.5 times greater, at least 2 times greater, or even more. In other embodiments, the chain-extended condensation polymers exhibit a higher viscosity at low shear rates and a lower viscosity at high shear rates than the condensation polymer formed in the absence of the chain extender.
  • the chain-extended condensation polymer exhibits a higher viscosity at shear rates below 400 s -1 , 300 s -1 , 200 s -1 , or less, and a lower viscosity at shear rates above 300 s -1 , 400 s -1 , 500 s -1 or more.
  • This characteristic may lead to improved processability of the chain-extended condensation polymers as compared to conventional condensation polymers since they would be expected to demonstrate low viscosity during extrusion, blow, and injection molding, but higher viscosity during low shear handling.
  • the chain extended condensation polymers also exhibit higher elasticity, increased die swell, increased stretch-ability during blow molding, higher melt tension, higher extensional viscosity, lower elastic modulus maintaining tensile strength and higher elongation at break ( i.e. higher toughness). This allows for faster processing during article manufacturing via injection-blow molding, extrusion-blow molding, sheet thermoforming, mono-oriented film, bi-oriented film, and fiber spinning.
  • articles formed from any of the disclosed chain-extended and processed, chain-extended condensation polymers include food or non-food contact containers, films, coatings, tapes, moldings, fibers, strapping, and other consumer products.
  • GMA is glycidyl methacrylate
  • STY is styrene
  • BA is butyl acrylate
  • 2-EHA is 2-ethylhexyl acrylate
  • MMA is methyl methacrylate.
  • PET Poly(ethylene terephthalate)
  • Chain Extenders Four epoxy functional chain extenders were produced using high temperature free radical continuous polymerization (SGO) as described above. The characterization details for these chain extenders are shown in Table 3. Table 3. Chain Extender Characterization Details. Chain Extender M n a M w a GMA STY BA 2-EHA MM A EEW b T g e Functionality d F n F w Units (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (g/eq) (°C) (epoxy/chain) Chain Extender 1 2,246 6,791 49.0 50.0 -- -- 1.0 285 55 7.9 23.8 Chain Extender 2 2,301 5,379 32.0 67.0 -- -- -- 1.0 445 59 5.2 12.1 Chain Extender
  • Epoxy equivalent weight (EEW) determined using perchloric acid titration method P-2-164.
  • DSC value defined as the midpoint of the first heat.
  • the molecular weights were measured using size exclusion chromatography (SEC) and are relative to polystyrene standards.
  • the compositions were estimated using a mass balance approach and were based on the gas chromatography (GC) characterization of the polymerization feed, distillate, and resin residuals.
  • the epoxy equivalent weights were determined using a perchloric acid titration method based on ASTM D 1652-90.
  • the glass transition temperatures were measured using differential scanning calorimetry (DSC) and were defined as the midpoint of the first heating cycle.
  • the number and weight average functionality per chain (Fn and Fw) were calculated by dividing the SEC number and weight average molecular weights (Mn and Mw) by the epoxy equivalent weight.
  • the chain extenders are chemically functionalized polymers that may be solid or liquid at room temperature.
  • Tg Glass Transition Temperature
  • Chain Extender 1 and Chain Extender 2 have a monomer composition and SEC molecular weight averages that make them solid at room temperature (Tg > 25°C).
  • copolymers with a low Tg may be prepared, resulting in liquid polymeric chain extenders.
  • the liquid chain extenders exhibit low viscosity at room temperature.
  • Chain Extenders 3 and 4 were designed with similar functionality to the two solid materials, Chain Extender 2 and Chain Extender 1, while having sufficiently low viscosity to be handled as liquids.
  • Chain Extenders 3 and 4 were designed to maximize the balance of molecular weight, functionality, and viscosity.
  • the ability of the chain extenders to be designed as solid or liquids gives additional advantages in the implementation of the proper feed stream for the chain extenders to be used in this in-reactor chain extension of polycondensates.
  • the chain extenders may be added to the esterification or melt polymerization reactor system as a solid to the proper solid addition port to prevent breaking vacuum in the esterification or melt polymerization reactor.
  • liquid chain extenders may be added or pumped into the melt polymerization or esterification reactors with conventional pumping equipment known in the art, without the need for the use of dilution solvents, which may be undesirable in the reaction mix.
  • the chain extenders may be added, either solid or liquid, as a solid concentrate (masterbatch) in a suitable plastic carrier. Using the same polycondensation polymer as a carrier in these concentrates avoids the introduction of foreign substances to the reactor system.
  • the chain extender is added, either solid or liquid, as a liquid dilution (liquid solution or liquid masterbatch) in a suitable liquid carrier. Using some liquid components in the system, such as monomers or reaction solvents, or reaction additives, as a liquid carrier in these liquid concentrates avoids introduction of foreign substances to the reactor system.
  • In-reactor chain extension includes adding one of the chain extenders, such as those exemplified and described in Table 3, during the polymerization process of PET or other polycondensate. Specifically, the chain extenders were added during the polycondensation stage of the batch polymerization process shown in Equation 2 of Scheme 1 at a predetermined time. The time was defined using a well-defined agitator torque, viscosity relationship, when the PET was at an SIV of 0.4 dL/g. The experiments are summarized in Table 4. With the exception of Example 3, the polymerizations were terminated at an SIV of 0.6 dL/g. Chain extender addition was accomplished using a pressurized stainless steel addition vessel having ball valves at both ends.
  • the granules were charged to the vessel, purged with nitrogen, and cooled to prevent melting during addition.
  • the addition vessel was attached to the top of the reactor, a nitrogen line attached to the top ball valve, and pressurized.
  • the reactor vacuum evacuated the vessel contents when the bottom ball valve was opened at the time of addition.
  • the ball valve was held open for sixty seconds, closed, and the top valve was opened to pressurize the vessel. After closing the top valve, the bottom valve was again opened to evacuate any remaining chain extender.
  • the liquids were heated for one hour prior to addition to reduce viscosity. Table 4. In-reactor Chain Extension Experimental Summary.
  • Example # Chain Extender Level Polymerization SIV a SSP SIV b (%, w/w) (dL/g) (dL/g) Control NA; Control NA 0.600 0.811 1 Chain Extender 1 0.10 0.601 0.809 2 Chain Extender 1 0.20 0.603 0.808 3 Chain Extender 1 0.20 0.720 0.840 4 Chain Extender 2 0.31 0.597 0.825 5 Chain Extender 3 0.32 0.595 0.779 6 Chain Extender 4 0.32 0.603 0.770 (a) solution intrinsic viscosity measured following polycondensation. (b) solution intrinsic viscosity measured after solid state polymerization. NA - not applicable.
  • Control Example was a linear PET control not subjected to chain extension.
  • the outcomes of all subsequent experimentation were compared to the Control Example.
  • Examples 1 and 2 used low and moderate chain extender concentrations, respectively, designed to define the typical polymerization time reduction that may be associated with Chain Extender 1 in-reactor chain extension. Decreased polymerization times may be used to increase plant efficiencies.
  • Example 3 was identical to Example 2 but polymerized to an SIV of about 0.700 dL/g, typical of that required for PET sheet. Such a polymer eliminates the need for any further costly SSP.
  • Example 4 involved the substitution of Chain Extender 1 with the lower functional Chain Extender 2 at equal epoxy equivalence. Lower functionality was expected to reduce haze associated with excessive branching or gel.
  • Example 5 involved the same experiment as Example 4 using the liquid chain extender Chain Extender 3, which is equivalent to Chain Extender 2 in terms of molecular weight and functionality.
  • the liquid chain extender was void of styrene monomer to increase food contact approval.
  • Example 6 involved the same experiment as Example 5, using the lower molecular weight liquid chain extender Chain Extender 4.
  • lbf is an abbreviation for pounds-force with 1 lbf equal to 4.45 Newtons.
  • a significant reduction in polymerization time was observed in both the agitator torque and speed traces. That is, the saw tooth and stair step pattern is offset to shorter times for the Example 1 and Example 2 when compared to Control Example. The offset of the Example 2 traces is greater than Example 1.
  • the actual reduction in polymerization time has been summarized in FIG. 3 .
  • FIG. 4 shows that 30 to 40% added capacity could be realized when Chain Extenders 1 and 2 are used at 0.3 and 0.2% (w/w), respectively.
  • the calculations apply to a 50,000 MT/yr batch polymerization where Stage 1 and Stage 2 are performed in separate reactors run in parallel.
  • MT is an abbreviation for thousand tons.
  • the rate limiting step in this process is the polycondensation step.
  • FIGs. 7 and 8 summarize the total process time to prepare 0.7 and 0.8 dL/g grade PET, respectively.
  • the time advantages illustrated in FIG. 6 could be applied to the preparation of fiber, film, and low end sheet (see Table 2).
  • Example 2 branching of the chain extended PET did appear to affect polymer rheology.
  • the melt viscosity of Control Example, Example 1, and Example 2 was studied and the results are shown in FIG. 8 .
  • the SIV for each of the materials was measured to be approximately 0.6 dL/g (see Table 4, column 5).
  • the viscosity traces were obtained using a cone and plate viscometer at 6.3 s -1 . At all temperatures, the viscosity of the chain extended materials were measured to be greater than the control. More specifically, the viscosity of Example 2 was twice that of Control Example at the similar SIV.
  • Solution intrinsic viscosity is a measure of the hydrodynamic volume of non-interacting polymer spheres ( i.e., infinite dilution) where polymer-solvent interactions are important. Whereas, melt viscosity is highly dependent upon polymer-polymer interactions. It is easy to imagine a set of linear and branched materials that have similar hydrodynamic radii and dilute solution behavior (e.g. , Control Example and Example 2). However, under bulk conditions the branched species having more points of interaction would demonstrate higher low shear viscosity as shown in FIG. 8 .
  • Viscosity at shear rates typically experienced during extrusion and low end blow and injection molding have been shown in FIG. 9 . Consistent with the melt viscosity results shown in FIG. 8 , higher viscosity was observed for the chain extended materials (Example 1 and Example 2) at low shear rates. At approximately 300s -1 a viscosity cross over was observed. The crossover indicates that the polymer-polymer interactions that dominate low shear viscosity can be disturbed under relatively mild conditions, suggesting weak interactions. This provides some insight into the processability of the chain-extended materials. The chain-extended materials may demonstrate low viscosity during extrusion, blow, and injection molding, but higher viscosity during low shear handling, resulting in improved processability.

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EP2456792A4 (en) 2012-12-19
EP2456792A2 (en) 2012-05-30
US8785558B2 (en) 2014-07-22
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ES2457552T3 (es) 2014-04-28
WO2011011498A3 (en) 2011-04-28
JP2016056384A (ja) 2016-04-21
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CN102844336A (zh) 2012-12-26
JP6180562B2 (ja) 2017-08-16

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